@prefix prodottidellaricerca: . @prefix istituto: . @prefix prodotto: . istituto:CDS020 prodottidellaricerca:prodotto prodotto:ID16683 . @prefix pubblicazioni: . @prefix unitaDiPersonaleInterno: . unitaDiPersonaleInterno:MATRICOLA16546 pubblicazioni:autoreCNRDi prodotto:ID16683 . @prefix unitaDiPersonaleEsterno: . unitaDiPersonaleEsterno:ID6678 pubblicazioni:autoreCNRDi prodotto:ID16683 . @prefix modulo: . modulo:ID2548 prodottidellaricerca:prodotto prodotto:ID16683 . modulo:ID2546 prodottidellaricerca:prodotto prodotto:ID16683 . @prefix rdf: . prodotto:ID16683 rdf:type prodotto:TIPO1101 . @prefix retescientifica: . prodotto:ID16683 rdf:type retescientifica:ProdottoDellaRicerca . @prefix rdfs: . prodotto:ID16683 rdfs:label "Stabilization of the Tautomers HP(OH)2 and P(OH)3 of Hypophosphorous and Phosphorous Acids as Ligands (Articolo in rivista)"@en . @prefix xsd: . prodotto:ID16683 pubblicazioni:anno "2006-01-01T00:00:00+01:00"^^xsd:gYear ; pubblicazioni:doi "10.1039/b510479c"^^xsd:string . @prefix skos: . prodotto:ID16683 skos:altLabel "
Akbayeva D.; Di Vaira M.; Seniori Costantini S.; Peruzzini M.; Stoppioni P. (2006)
Stabilization of the Tautomers HP(OH)2 and P(OH)3 of Hypophosphorous and Phosphorous Acids as Ligands
in Dalton transactions (2003. Print)
"^^rdf:HTML ; pubblicazioni:autori "Akbayeva D.; Di Vaira M.; Seniori Costantini S.; Peruzzini M.; Stoppioni P."^^xsd:string ; pubblicazioni:paginaInizio "389"^^xsd:string ; pubblicazioni:paginaFine "395"^^xsd:string . @prefix ns12: . prodotto:ID16683 pubblicazioni:rivista ns12:ID74960 ; skos:note "ISI Web of Science (WOS)"^^xsd:string ; pubblicazioni:affiliazioni "ICCOM- CNR\nUniversit\u00E0 di Firenze, Dipartimento di Chimica"^^xsd:string ; pubblicazioni:titolo "Stabilization of the Tautomers HP(OH)2 and P(OH)3 of Hypophosphorous and Phosphorous Acids as Ligands"^^xsd:string ; prodottidellaricerca:abstract "Treatment of [CpRu(PPh3)2Cl] 1 with the stoichiometric amount of H3PO2 or H3PO3 in the presence of\nchloride scavengers (AgCF3SO3 or TlPF6) yields compounds of formula [CpRu(PPh3)2(HP(OH)2)]Y\n(Y = CF3SO3 2a or PF6 2b) and [CpRu(PPh3)2(P(OH)3)]Y (Y = CF3SO3 3a or PF6 3b) which contain,\nrespectively, the HP(OH)2 and P(OH)3 tautomers of hypophosphorous and phosphorous acids bound\nto ruthenium through the phosphorus atom. The triflate derivatives 2a and 3a react further with\nhypophosphorous or phosphorous acids to yield, respectively, the complexes [CpRu(PPh3)(HP(OH)2)2]-\nCF3SO3 4 and [CpRu(PPh3)(P(OH)3)2]CF3SO3 5 which are formed by substitution of one molecule of\nthe acid for a coordinated triphenylphosphine molecule. The compounds 2 and 3 are quite stable in the\nsolid state and in solutions of common organic solvents, but the hexafluorophosphate derivatives\nundergo easy transformations in CH2Cl2: the hypophosphorous acid complex 2b yields the compound\n[CpRu(PPh3)2(HP(OH)2)]PF2O2 6, whose difluorophosphate anion originates from hydrolysis of PF6\n-;\nthe phosphorous acid complex 3b yields the compound [CpRu(PPh3)2(PF(OH)2)]PF2O2 7, which is\nproduced by hydrolysis of hexafluorophosphate and substitution of a fluorine for an OH group of the\ncoordinated acid molecule. All the compounds have been characterized by elemental analyses and\nNMR measurements. The crystal structures of 2a, 3a and 7 have been determined by X-ray diffraction\nmethods.\nIntroduction\nThe hypophosphorous and phosphorous acids (systematic names\nphosphinic and phosphonic acid, respectively) have tetrahedral\nstructures, [H2PO(OH)]1 and [HPO(OH)2]2 with two and, respectively,\none hydrogen atom directly bound to the phosphorus.\nThe hypophosphorous acid therefore acts as a relatively strong\nmonobasic acid (pKa = 1.24),3 yielding hypophosphites [H2PO2]-;\nthe phosphorous acid is dibasic and its completely deprotonated\nanion is [HPO3]2-.The coordination properties of the above species\nhave been seldom considered and the sparse results suggest that\nthe acids and their anions act as ligands via their oxygen atoms,\nwhile the phosphorus atom is devoid of donor properties, lacking a\nlone pair.4 Both hypophosphorous and phosphorous acids exhibit\ntautomeric equilibria between tetrahedral (a) and pyramidal (b)\nstructures (Scheme 1) and it is well established that the phosphoryl\ntautomer (a) predominates.5 Accordingly, it has been difficult to\ntrace the less stable tautomer (b) of each acid. They have been\npostulated as intermediates in some palladium catalytic reactions6\nand in the oxidation of phosphorous acid by metals.7 Recently\nthe (b) tautomeric form of both hypophosphorous8 and the\nphosphorous9 acid has been stabilized by coordination to nickel\nand palladium inM3M?Q4(H2O)9 (M =Mo, W; M? = Ni, Pd; Q =\naDipartimento di Chimica, Universit`a di Firenze, via della Lastruccia n. 3,\n50019, Sesto Fiorentino, Firenze, Italy. E-mail: piero.stoppioni@unifi.it\nbICCOM CNR, Via Madonna del Piano, snc-50019, Sesto Fiorentino,\nFirenze, Italy. Email: mperuzzini@iccom.cnr.it\nScheme 1"@en ; prodottidellaricerca:prodottoDi modulo:ID2548 , istituto:CDS020 , modulo:ID2546 ; pubblicazioni:autoreCNR unitaDiPersonaleEsterno:ID6678 , unitaDiPersonaleInterno:MATRICOLA16546 . ns12:ID74960 pubblicazioni:rivistaDi prodotto:ID16683 .